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US7709155B2 - Nonaqueous electrolytic solution and lithium-ion secondary battery - Google Patents

Nonaqueous electrolytic solution and lithium-ion secondary battery Download PDF

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US7709155B2
US7709155B2 US10/558,556 US55855604A US7709155B2 US 7709155 B2 US7709155 B2 US 7709155B2 US 55855604 A US55855604 A US 55855604A US 7709155 B2 US7709155 B2 US 7709155B2
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lithium
electrolytic solution
nonaqueous electrolytic
ion secondary
anode
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US20070015063A1 (en
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Kazuya Ogawa
Atsushi Sano
Tsuyoshi Iijima
Satoshi Maruyama
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TDK Corp
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TDK Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a nonaqueous electrolytic solution and a lithium-ion secondary battery.
  • lithium-ion secondary batteries have widely been employed as power supplies for portable devices because of their very high energy density and the like.
  • a lithium-ion secondary battery is mainly constituted by a cathode, an anode, a separator, and a nonaqueous electrolytic solution, whereas various studies have been made in order to further improve battery characteristics.
  • a nonaqueous solvent for the nonaqueous electrolytic solution is one having a relatively low melting point, a relatively high conductivity, a relatively wide potential window (electrochemical window), and a capability of yielding a high ionic conductivity even at a low temperature when an electrolyte is dissolved.
  • propylene carbonate has favorably been in use.
  • a negative electrode anode
  • a carbon material such as highly crystallized graphite as a constituent material
  • propylene carbonate has been problematic in that its decomposition proceeds in a cathode (an electrode which functions as a negative electrode at the time of discharging) at the time of charging in particular.
  • batteries aimed at restraining the decomposition reaction of propylene from proceeding by adding 1,3-propane sultone or 1,4-butane sultone into a nonaqueous electrolytic solution using at least propylene carbonate as an ingredient of the nonaqueous solvent have been proposed (see, for example, Japanese Patent Application Laid-Open Nos. 2000-3724 and 2000-3725).
  • batteries aimed at restraining the decomposition reaction of propylene carbonate from progressing by adding vinylene carbonate into a nonaqueous electrolytic solution using at least propylene carbonate as an ingredient of the nonaqueous solvent have been proposed (see, for example, Japanese Patent Application Laid-Open Nos. HEI 11-67266 and 2000-58125).
  • the inventors have found that, when provided with a negative electrode using a carbon material having a high degree of graphitization as a constituent material, the conventional lithium-ion secondary batteries disclosed in Japanese Patent Application Laid-Open Nos. 2000-3724, 2000-3725, and HEI 10-339850 mentioned above can form a decomposition-suppressing film for propylene carbonate, but the chemical stability of the film is insufficient, whereby a sufficient charging/discharging cycle characteristic is not obtained.
  • the inventors have also found that, when provided with a negative electrode using a carbon material having a high degree of graphitization as a constituent material, the conventional lithium-ion secondary batteries disclosed in Japanese Patent Application Laid-Open Nos. HEI 11-67266 and 2000-58125 mentioned above improve the charging/discharging cycle characteristic since they can form a decomposition-restraining film having a relatively high chemical stability for propylene carbonate, but fail to attain a sufficient high-rate discharging characteristic.
  • the inventors have found that these batteries also generate a gas when a reduction product of a cathode for charging (negative electrode for discharging) is oxidized at an anode for charging (positive electrode for discharging), so that the gas generation is not sufficiently suppressed when the batteries are stored or caused to generate power at a high temperature (40 to 100° C.) in particular.
  • a high temperature 40 to 100° C.
  • the case When a case is formed from a film in particular, the case may expand during its use or storage, or a sealing part of the case may peel off, thereby causing leakage, thus failing to achieve a sufficient reliability.
  • the inventors have found that the conventional lithium-ion secondary battery disclosed in Japanese Patent Application Laid-Open No. 2001-43895 can attain an effect of restraining the decomposition reaction of propylene carbonate from proceeding, for example, such that the gas generation can be suppressed even when provided with a negative electrode using a carbon material having a high degree of graphitization as a constituent material, but incurs the following problem. Namely, this battery fails to attain a sufficient charging/discharging cycle characteristic.
  • the inventors conducted diligent studies in order to achieve the above-mentioned object and, as a result, have found that, when 1,3-propane sultone (which will hereinafter be referred to as “PS” when necessary) and vinylene carbonate (which will hereinafter be referred to as “VC” when necessary) are added into a nonaqueous electrolytic solution using at least propylene carbonate as an ingredient of a nonaqueous solvent, the chemical stability of a protective film generated on the surface of a negative electrode as each of PS and VC is decomposed heavily depends on respective contents of PS and VC in the nonaqueous electrolytic solution and the ratio between the respective amounts of addition of PS and VC.
  • PS 1,3-propane sultone
  • VC vinylene carbonate
  • the inventors have further found it quite effective in achieving the above-mentioned object to regulate the ingredient composition of the nonaqueous solvent in the nonaqueous electrolytic solution so as to satisfy the following condition, thereby attaining the present invention.
  • the present invention provides a nonaqueous electrolytic solution including a nonaqueous solvent and a lithium salt soluble in the nonaqueous solvent; wherein the nonaqueous solvent contains propylene carbonate, a first compound expressed by the following general formula (I), and a second compound expressed by the following general formula (II); wherein the content of propylene carbonate in the nonaqueous solvent is at least 10 volume %; and wherein the content X [mass %] of the first compound and the content Y [mass %] of the second compound simultaneously satisfy the conditions represented by the following expressions (1) and (2): 2 ⁇ ( X+Y ) ⁇ 8 (1) 0.01 ⁇ ( Y/X ) ⁇ 0.30 (2)
  • R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are either identical to or different from each other, indicating any of a hydrogen atom and hydrocarbon groups having a carbon number of 1 to 3;
  • R 7 and R 8 are either identical to or different from each other, indicating any of a hydrogen atom and hydrocarbon groups having a carbon number of 1 to 6.
  • the nonaqueous electrolytic solution of the present invention uses a nonaqueous solvent having an ingredient configuration simultaneously satisfying the conditions mentioned above, and thus can yield the following effect when used as an electrolyte for a lithium-ion secondary battery. Namely, it can easily and reliably construct a lithium-ion secondary battery capable of attaining excellent initial power generation efficiency, high-rate discharging characteristic, low-temperature discharging characteristic, and charging/discharging cycle characteristic, while being able to achieve an excellent reliability even when stored or caused to generate power within the range of 40 to 100° C.
  • Satisfying the condition of expression (1) can improve the initial power generation efficiency, the high-rate discharging characteristic, and the discharging characteristic at a low temperature ( ⁇ 20 to +25° C.) in particular.
  • Satisfying the condition of (2) can improve the charging/discharging cycle in particular, whereby gases can fully be restrained from occurring within a case when the battery is stored or caused to generate power within the range of 40 to 100° C. Satisfying the conditions of expressions (1) and (2) at the same time can Yield the above-mentioned effect of the present invention without lowering any of the characteristics mentioned above.
  • the content X [mass %] of the first compound does not refer to the content of the first compound in the nonaqueous solvent, but the content based on the total mass of the finally obtained nonaqueous electrolytic solution.
  • the content Y [mass %] of the second compound does not refer to the content of the first compound in the nonaqueous solvent, but the content based on the total mass of the finally obtained nonaqueous electrolytic solution.
  • the content of propylene carbonate in the nonaqueous solvent is 10 to 60 volume % in the present invention.
  • the content of PC exceeds 60 volume %, the decomposition reaction of PC is easier to proceed.
  • the nonaqueous solvent further contains ethylene carbonate whose content is 1 to 20 volume % in the present invention.
  • ethylene carbonate which will hereinafter be referred to as “EC” when necessary
  • the decomposition reaction of PC is easier to proceed when the content of EC is less than 1 volume %.
  • the content of EC exceeds 20 volume %, a sufficient charging/discharging characteristic is less likely to be obtained at a low temperature ( ⁇ 20 to +25° C.).
  • the nonaqueous solvent further contains a chain carbonate whose content is 30 to 85 volume %.
  • a sufficient high-rate discharging characteristic is less likely to be obtained when the content of chain carbonate is less than 30 volume %.
  • a sufficient high-rate discharging characteristic is less likely to be obtained at a low temperature ( ⁇ 20 to +25° C.).
  • a sufficient charging capacity is less likely to be obtained.
  • the chain carbonate is diethyl carbonate (which will hereinafter be referred to as “DEC” when necessary) and/or ethylmethyl carbonate (which will hereinafter be referred to as “EMC” when necessary).
  • R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 in the first compound are hydrogen atoms in the present invention.
  • the first compound is preferably 1,3-propane sultone.
  • R 7 and R 8 in the second compound are hydrogen atoms in the present invention.
  • the second compound is preferably vinylene carbonate.
  • the nonaqueous electrolytic solution of the present invention may be gelled by a gelling agent. This can construct a so-called lithium-ion polymer secondary battery.
  • the present invention also provides a lithium-ion secondary battery comprising, at least, an anode, a cathode, an insulating separator disposed between the anode and cathode, a nonaqueous electrolytic solution containing a lithium salt, and a case accommodating the anode, cathode, separator, and a nonaqueous electrolytic solution in a closed state; wherein the nonaqueous electrolytic solution is any of the nonaqueous electrolytic solutions in accordance with the present invention mentioned above.
  • the lithium-ion secondary battery of the present invention is configured so as to include the nonaqueous electrolytic solution of the present invention mentioned above, and thus can achieve excellent initial power generation efficiency, high-rate discharging characteristic, and charging/discharging cycle characteristic, while being able to attain an excellent reliability even when stored or caused to generate power within the range of 40 to 100° C.
  • electrodes to act as the anode and cathode become a reaction field capable of reversibly advancing an electron transfer reaction in which a lithium ion (or metal lithium) is involved as a redox species.
  • reversibly advancing an electron transfer reaction refers to reversibly advancing the above-mentioned electron transfer reaction within a battery life required for a power supply or auxiliary power supply of a device to which the battery is mounted.
  • Anode active materials contained as a constituent material in the anode and cathode active materials contained as a constituent material in the cathode refer to materials contributing to the above-mentioned electron transfer reaction.
  • the anode active materials and cathode active materials may be carbon materials or metal oxides having structures which can reversibly proceed with occlusion/release of lithium ions or desorption/insertion (intercalation) of lithium ions.
  • a material capable of reversibly proceeding with doping/undoping of lithium ions with their counter anions (e.g., ClO 4 ⁇ ), such as a conductive polymer, may also be used as an anode active material and/or cathode active material singly or together with other active materials.
  • anode in “anode active material” is one (negative electrode active material) based on its polarity at the time of discharging the battery
  • cathode in “cathode active material” is also one (positive electrode active material) based on its polarity at the time of discharging the battery. Specific examples of the anode active material and cathode active material will later be explained.
  • the case is formed from a flexible film (which will hereinafter be referred as “film”), and is formed by using at least a pair of films opposing each other, whereas the film is preferably a composite package film comprising, at least, an innermost layer made of a synthetic resin in contact with the nonaqueous electrolytic solution and a metal layer disposed above the innermost layer, i.e., on the outside of the innermost layer.
  • film a flexible film
  • the film is preferably a composite package film comprising, at least, an innermost layer made of a synthetic resin in contact with the nonaqueous electrolytic solution and a metal layer disposed above the innermost layer, i.e., on the outside of the innermost layer.
  • the lithium-ion secondary battery itself can be formed like a thin film. This can easily improve the original volume energy density and the energy density per unit volume of a space where the lithium-ion secondary battery is to be placed (which will hereinafter be referred to as “volume energy density based on the volume of the space to place”).
  • the “volume energy density” of the lithium-ion secondary battery is originally defined by the ratio of the total output energy with respect to the whole volume of the part contributing to power generation constituted by the electrodes and separator (i.e., “matrix” which will be explained later) of the lithium-ion secondary battery or the whole volume thereof including its container.
  • the “volume energy density based on the volume of the space to place” refers to the ratio of the total output energy of the lithium-ion secondary battery with respect to an apparent volume of the lithium-ion secondary battery determined according to the maximum length, maximum width, and maximum thickness thereof.
  • the case is not limited to one formed from the above-mentioned composite package film, but may be a case made of a metal such as a metal can shell.
  • a metal such as a metal can shell.
  • the latter can be employed in uses where the case requires a mechanical strength higher than that of the composite package film.
  • each of the anode and cathode has a planar form and contains an electronically conductive porous body as a constituent material
  • the separator has a planar form and is made of an insulating porous body
  • the nonaqueous electrolytic solution is at least partly contained within the anode, cathode, and separator.
  • Employing such a configuration can further improve the volume energy density based on the volume of the space to place.
  • the above-mentioned “planar” state encompasses flat and curved planar states as well.
  • FIG. 1 is a front view showing a preferred embodiment of the lithium-ion secondary battery in accordance with the present invention
  • FIG. 2 is an unfolded view of the inside of the lithium-ion secondary battery shown in FIG. 1 as seen in a direction normal to a surface of an anode;
  • FIG. 3 is a schematic sectional view of the lithium-ion secondary battery shown in FIG. 1 taken along the line X 1 -X 1 of FIG. 1 ;
  • FIG. 4 is a schematic sectional view showing a major part of the lithium-ion secondary battery shown in FIG. 1 taken along the line X 2 -X 2 of FIG. 1 ;
  • FIG. 5 is a partly broken side view of the lithium-ion secondary battery shown in FIG. 1 ;
  • FIG. 6 is a schematic sectional view showing an example of basic configuration of a film constituting a case of the lithium-ion secondary battery shown in FIG. 1 ;
  • FIG. 7 is a schematic sectional view showing another example of basic configuration of the film constituting the case of the lithium-ion secondary battery shown in FIG. 1 ;
  • FIG. 8 is a schematic sectional view showing an example of basic configuration of the anode in the lithium-ion secondary battery shown in FIG. 1 and
  • FIG. 9 is a schematic sectional view showing an example of basic configuration of the cathode in the lithium-ion secondary battery shown in FIG. 1 .
  • FIG. 1 is a front view showing a preferred embodiment of the lithium-ion secondary battery in accordance with the present invention.
  • FIG. 2 is an unfolded view of the inside of the lithium-ion secondary battery shown in FIG. 1 as seen in a direction normal to a surface of an anode 10 .
  • FIG. 3 is a schematic sectional view of the lithium-ion secondary battery shown in FIG. 1 taken along the line X 1 -X 1 of FIG. 1 .
  • FIG. 4 is a schematic sectional view showing a major part of the lithium-ion secondary battery shown in FIG. 1 taken along the line X 2 -X 2 of FIG. 1 .
  • FIG. 5 is a partly broken side view of the lithium-ion secondary battery shown in FIG. 1 , whereas its partial section illustrates a major part taken along the line Y-Y of FIG. 1 .
  • the lithium-ion secondary battery 1 is mainly constituted by the planar anode 10 and a planar cathode 20 which oppose each other, a planar separator 40 disposed between the anode 10 and cathode 20 adjacent to both of the anode 10 and cathode 20 , a nonaqueous electrolytic solution 30 , a case 50 accommodating them in a closed state, an anode lead 12 having one end part electrically connected to the anode 10 and the other end part projecting out of the case 50 , and a cathode lead 22 having one end part electrically connected to the cathode 20 and the other end part projecting out of the case 50 .
  • the “anode” 10 and “cathode” 20 are determined according to their polarities at the time when discharging the lithium-ion secondary battery 1 . Therefore, the “anode 10 ” and “cathode 20 ” become “cathode” and “anode,” respectively, at the time of charging.
  • the lithium-ion secondary battery 1 has a configuration which will be explained in the following.
  • the case 50 comprises a pair of films (first film 51 and second film 52 ) which oppose each other. As shown in FIG. 2 , the first film 51 and second film 52 in this embodiment are connected to each other. Namely, a rectangular film made of a single composite package film is folded at a fold line X 3 -X 3 shown in FIG. 2 , and a pair of opposing fringes of the rectangular film (a fringe 51 B of the first film 51 and a fringe 52 B of the second film 52 in the drawing) are overlaid on each other and sealed with an adhesive or by heat, whereby the case 50 in this embodiment is formed.
  • the first film 51 and second film 52 represent respective film parts having surfaces opposing each other when a single rectangular film 53 is folded as mentioned above.
  • first film 51 and second film 52 are obtained when the single rectangular film 53 is folded as mentioned above, no margins for connecting the first film 51 and second film 52 to each other are required at the part of fold line X 3 -X 3 . This can further reduce seal parts in the case 50 . As a result, the energy density based on the volume of a space where the lithium-ion secondary battery 1 is to be placed can further be improved.
  • respective one ends of the anode lead 12 connected to the anode 10 and the cathode lead 22 are arranged so as to project out of the seal part where the fringe 51 B of the first film 51 and the fringe 52 B of the second film are connected to each other.
  • the film constituting the first film 51 and second film 52 is a flexible film as mentioned above. Since the film is light in weight and can easily be formed into a thin film, the lithium-ion secondary battery itself can be formed into a thin film. This can easily improve the original volume energy density of the lithium-ion secondary battery 1 , and the volume energy density based on the volume of the space where the lithium-ion secondary battery 1 is to be placed.
  • the first film 51 and second film 52 are not restricted in particular as long as they are flexible films.
  • the films are preferably a “composite package film” comprising, at least, an innermost layer made of a synthetic resin in contact with the nonaqueous electrolytic solution 30 , and a metal layer disposed on one side of the innermost layer, i.e., on the outside of the innermost layer.
  • Examples of composite package films usable as the first film 51 and second film 52 include those having the configurations shown in FIGS. 6 and 7 .
  • the composite package film 53 shown in FIG. 6 comprises an innermost layer 50 a made of a synthetic resin in contact with the nonaqueous electrolytic solution by its inner face F 53 , and a metal layer 50 c disposed on the other surface (outer face) of the innermost layer 50 a .
  • the composite package film 54 shown in FIG. 7 has a configuration in which an outermost layer 50 b made of a synthetic resin is further disposed on the outer face of the metal layer 50 c in the composite package film 53 shown in FIG. 6 , i.e., on the side of the metal layer 50 c opposite from the innermost layer 50 a.
  • the composite package film usable as the first film 51 and second film 52 is not limited in particular as long as it is a composite package film comprising at least two layers composed of at least one synthetic resin layer such as the above-mentioned innermost layer, and a metal layer made of a metal foil or the like.
  • the film is constituted by at least three layers comprising the innermost layer 50 a , the outermost layer 50 b made of a synthetic resin disposed on the outer surface side of the case 50 farthest from the innermost layer 50 a , and at least one metal layer 50 c disposed between the innermost layer 50 a and outermost layer 50 b as with the composite package film 54 shown in FIG. 7 .
  • the innermost layer 50 a is a flexible layer.
  • the constituent material of this layer is not limited in particular as long as it is a synthetic resin which can exhibit the flexibility mentioned above and has chemical stability (property of causing no chemical reaction, no dissolution, and no swelling) with respect to the nonaqueous electrolytic solution 30 in use and chemical stability with respect to oxygen and water (moisture in the air).
  • Preferred is a material further having a property of low permeability to oxygen, water (moisture in the air), and components of the nonaqueous electrolytic solution 30 .
  • Examples of such a synthetic resin include engineering plastics and thermoplastic resins such as polyethylene, polypropylene, acid-denatured polyethylene, acid-denatured polypropylene, polyethylene ionomers, and polypropylene ionomers.
  • “engineering plastics” refer to plastics having such excellent kinetic characteristics, heat resistance, and durability as to be usable in mechanical components, electric components, housing materials, and the like, examples of which include polyacetal, polyamide, polycarbonate, polyoxytetramethylene oxyterephthaloyl (polybutylene terephthalate), polyethylene terephthalate, polyimide, and polyphenylene sulfide.
  • this synthetic resin layer may use a constituent material similar to that of the innermost layer 50 a.
  • the metal layer 50 c is a layer made of a metal material having an anticorrosion property against oxygen, water (moisture in the air), and the nonaqueous electrolytic solution.
  • Metal foils made of aluminum, aluminum alloys, titanium, and chromium, for example, may also be used as the metal layer 50 c.
  • the method of sealing all the fringes 51 B and 52 B in the case 50 is preferably heat sealing from the viewpoint of productivity.
  • FIG. 8 is a schematic sectional view showing an example of basic configuration of the anode in the lithium-ion secondary battery 1 shown in FIG. 1 .
  • FIG. 9 is a schematic sectional view showing an example of basic configuration of the cathode in the lithium-ion secondary battery shown in FIG. 1 .
  • the anode 10 is constituted by a collector 16 and an anode active material containing layer 18 formed on the collector 16 .
  • the cathode 20 is constituted by a collector 26 and a cathode active material containing layer 28 formed on the collector 26 .
  • the collectors 16 and 26 are not restricted in particular as long as they are conductors which can sufficiently transfer electric charges to the anode active material containing layer 18 and cathode active material containing layer 28 , respectively, whereby known collectors used in lithium-ion secondary batteries can be employed.
  • Examples of the collectors 16 and 26 include foils of metals such as aluminum and copper.
  • the anode active material containing layer 18 of the anode 10 is mainly constituted by an anode active material, a conductive auxiliary agent, and a binder.
  • the anode active material is not restricted in particular as long as it can reversibly proceed with occlusion/release of lithium ions, desorption/insertion (intercalation) of lithium ions, or doping/undoping of lithium ions with their counter anions (e.g., ClO 4 ⁇ ), whereby known anode active materials can be used.
  • Examples of such an active material include carbon materials such as natural graphite, artificial graphite, mesocarbon microbeads, mesocarbon fiber (MCF), coke, glassy carbon, and fired organic carbons, metals such as Al, Si, and Sn which are combinable with lithium, amorphous compounds mainly composed of oxides such as SiO 2 and SnO 2 , and lithium titanate (Li 4 Ti 5 O 12 ).
  • carbon materials More preferred are those having an interlayer distance d 002 of 0.335 to 0.338 nm and a crystallite size Lc 002 of 30 to 120 nm.
  • Examples of carbon materials satisfying such conditions include artificial graphite and MCF (mesocarbon fiber).
  • the above-mentioned interlayer distance d 002 and crystallite size Lc 002 can be determined by X-ray diffraction.
  • the present invention can sufficiently suppress the decomposition of propylene carbonate by employing the nonaqueous electrolytic solution 30 as a constituent.
  • the conductive auxiliary agent is not restricted in particular, whereby known conductive auxiliary agents can be used.
  • Examples of the conductive auxiliary agent include carbon blacks; carbon materials; fine powders of metals such as copper, nickel, stainless, and iron; mixtures of the carbon materials and fine powders of metals; and conductive oxides such as ITO.
  • the binder is not restricted in particular as long as it can bind particles of the anode active material and particles of the conductive auxiliary agent to each other.
  • the binder include fluorine resins such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), tetrafluoroethylene/hexafluoropropylene copolymer (FEP), tetrafluoroethylene/perfluoroalkylvinylether copolymer (PFA), ethylene/tetrafluoroethylene copolymer (ETFE), polychlorotrifluoroethylene (PCTFE), ethylene/chlorotrifluoroethylene copolymer (ECTFE), and polyvinyl fluoride (PVF); and styrene/butadiene rubber (SBR).
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • FEP tetrafluoroethylene/hexafluoro
  • the anode active material containing layer 18 contains an electronically conductive porous body.
  • the electronically conductive porous body include carbon materials (e.g., activated carbon) obtained by activating coking coke (e.g., petroleum coke manufactured by a delayed coker from material oils such as bottom oils of fluidized catalytic crackers for petroleum-based heavy oils and residual oils of vacuum distillers).
  • the cathode active material containing layer 28 of the cathode 20 is mainly constituted by a cathode active material, a conductive auxiliary agent, and a binder as with the anode active material containing layer 18 .
  • the cathode active material is not restricted in particular as long as it can reversibly proceed with occlusion/release of lithium ions, desorption/insertion (intercalation) of lithium ions, or doping/undoping of lithium ions with their counter anions (e.g., ClO 4 ⁇ ), whereby known anode active materials can be used.
  • the constituent materials other than the cathode active material contained in the cathode active material containing layer 28 materials similar to those constituting the anode active material containing layer 18 can be used as well.
  • the binder contained in the cathode active material containing layer 28 contributes not only to binding particles of the cathode active material and particles of the conductive auxiliary agent to each other as mentioned above, but also to binding them to the foil (collector 26 ). It will also be preferred if the cathode active material containing layer 28 contains an electronically conductive porous body.
  • the collector 28 of the cathode 20 is electrically connected to one end of the cathode lead 22 made of aluminum, for example, whereas the other end of the cathode lead 22 projects out of the case 50 .
  • the collector 18 of the anode 10 is electrically connected to one end of the anode lead 12 made of copper or nickel, for example, whereas the other end of the anode lead 12 projects out of the case 50 .
  • the separator 40 disposed between the anode 10 and cathode 20 is not restricted in particular as long as it is formed from an insulating porous body, whereby known separators used in lithium-ion secondary batteries can be employed.
  • the insulating porous body in the separator 40 include laminates of films made of polyethylene, polypropylene, and polyolefin, extended films of mixtures of the resins mentioned above, and fibrous nonwoven fabrics made of at least one species of constituent material selected from the group consisting of cellulose, polyester, and polypropylene.
  • the inner space of the case 50 is filled with the nonaqueous electrolytic solution 30 , which is partly contained within the anode 10 , cathode 20 , and separator 40 .
  • the nonaqueous electrolytic solution 30 is one in which a lithium salt is dissolved in an organic solvent.
  • lithium ion employed examples include salts such as LiPF 6 , LiClO 4 , LiBF 4 , LiAsF 6 , LiCF 3 SO 3 , LiCF 3 CF 2 SO 3 , LiC(CF 3 SO 2 ) 3 , LiN(CF 3 SO 2 ) 2 , LiN(CF 3 CF 2 SO 2 ) 2 , LiN(CF 3 SO 2 )(C 4 F 9 SO 2 ), and LiN(CF 3 CF 2 CO) 2 .
  • These salts may be used singly or in combination of two or more species.
  • the nonaqueous electrolytic solution 30 may be gelled by a gelling agent such as a gel polymer added thereto.
  • the nonaqueous solvent contains, at least, PC, a first compound expressed by the following general formula (I), and a second compound expressed by the following general formula (II), whereas it will be preferred if EC and a chain carbonate (which is preferably DEC) are further added thereto.
  • the content of propylene carbonate in the nonaqueous solvent is adjusted to 10 volume % or more, preferably 10 to 60 volume %.
  • the EC content is preferably adjusted to 1 to 20 volume %.
  • the chain carbonate (which is preferably DEC) is added, the chain carbonate content is preferably adjusted to 30 to 85 volume %.
  • R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are either identical to or different from each other, indicating any of a hydrogen atom and hydrocarbon groups having a carbon number of 1 to 3. It will be preferred in particular if the compound represented by the above-mentioned general formula (I) is 1,3-propane sultone in which all of R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are hydrogen atoms.
  • R 7 and R 8 are either identical to or different from each other, indicating any of a hydrogen atom and hydrocarbon groups having a carbon number of 1 to 6. It will be preferred in particular if the compound represented by the above-mentioned general formula (II) is vinylene carbonate in which all of R 7 and R 8 are hydrogen atoms.
  • the content X [mass %] of the first compound and the content Y [mass %] of the second compound are regulated so as to simultaneously satisfy the conditions represented by the following expressions (1) and (2): 2 ⁇ ( X+Y ) ⁇ 8 (1) 0.01 ⁇ ( Y/X ) ⁇ 0.30 (2)
  • the part of the anode lead 12 coming into contact with the seal part constituted by the fringe 51 B of the first film 51 and the fringe 52 B of the second film 52 is covered with an insulator 14 for preventing the anode lead 12 and the metal layer 50 c in the composite package film constituting the individual films from coming into contact with each other.
  • the part of the cathode lead 22 coming into contact with the seal part constituted by the fringe 51 B of the first film 51 and the fringe 52 B of the second film 52 is covered with an insulator 24 for preventing the cathode lead 22 and the metal layer 50 c in the composite package film constituting the individual films from coming into contact with each other.
  • the configurations of the insulators 14 and 24 are not restricted in particular. They may be formed from synthetic resins, for example. If the metal layer 50 c in the composite package film can sufficiently be prevented from coming into contact with the anode lead 12 and cathode lead 22 , the insulators 14 and 24 may be omitted.
  • the above-mentioned lithium-ion secondary battery 1 can attain excellent initial power generation efficiency, high-rate discharging characteristic, and charging/discharging cycle characteristic even when the anode active material containing layer 18 included in the anode 10 is constituted by a carbon material including graphite. Also, the lithium-ion secondary battery 1 can sufficiently restrain gases from occurring even when stored or caused to generate power within the range of 40 to 100° C. Therefore, when the case 50 is formed from a film in particular, the case 50 is fully prevented from expanding and causing leakage from its seal part during the use or storage of the battery 1 . Therefore, the lithium-ion secondary battery 1 can yield an excellent reliability.
  • the method of manufacturing a matrix 60 is not limited in particular, whereby known methods employed in the manufacture of known lithium-ion secondary batteries can be used.
  • the above-mentioned constituents are mixed and then dispersed into a solvent adapted to dissolve the binder, so as to make an electrode forming coating liquid (slurry or the like).
  • the solvent is not restricted in particular as long as it is adapted to dissolve the binder and disperse the conductive auxiliary agent.
  • N-methyl-2-pyrrolidone and N,N-dimethylformamide can be used.
  • the above-mentioned electrode forming coating liquid is applied onto respective surfaces of the collectors 16 and 26 , and are dried and extended, so as to form active material containing layers 18 , 28 on their corresponding collectors 16 and 26 .
  • the making of the anode 10 and cathode 20 is completed.
  • the technique for applying the electrode forming coating liquid onto the surfaces of collectors 16 and 26 is not restricted in particular, and may be determined appropriately according to the material, form, and the like of the collectors 16 and 26 . Examples of the technique include metal mask printing, electrostatic coating, dip coating, spray coating, roll coating, doctor blading, gravure coating, and screen printing.
  • the anode lead 12 and cathode lead 22 are electrically connected to thus prepared anode 10 and cathode 20 , respectively.
  • the separator 40 is disposed between the anode 10 and cathode 20 while in contact therewith (in a nonbonding state), whereby the matrix 60 is completed.
  • a film to become a layer made of a synthetic resin and a metal foil made of aluminum or the like which constitute a composite package film are prepared, for example.
  • the metal foil can be prepared by extending a metal material, for example.
  • the metal foil is bonded by way of an adhesive onto the film to become the synthetic resin layer, and so forth, so as to yield the above-mentioned configuration preferably composed of a plurality of layers, thereby making a composite package film (multilayer film).
  • the composite package film is cut into a predetermined size, so as to prepare a single rectangular film.
  • the first film 51 and second film 52 are connected to each other.
  • the single film 53 is folded, and the fringe 51 B of the first film 51 and the fringe 52 B of the second film 52 are heat-sealed by a desirable seal width with a sealer under a predetermined heating condition, for example.
  • a sealer under a predetermined heating condition, for example.
  • a part is left without being heat-sealed. This yields the case 50 with an opening.
  • the matrix 60 having the anode lead 12 and cathode lead 22 electrically connected thereto is inserted into the case 50 in the state provided with the opening. Thereafter, the nonaqueous electrolytic solution 30 is injected. Subsequently, while the anode lead 12 and cathode lead 22 are partly inserted in the case 50 , the opening of the case 50 is sealed with a sealer, whereby the anode 10 , cathode 20 , separator 40 , and nonaqueous electrolytic solution 30 are accommodated in the case 50 in a closed state. Thus, the making of the case 50 and lithium-ion secondary battery 1 is completed.
  • the lithium-ion secondary battery of the present invention is not limited to one having such a form, but may have a cylindrical form or the like.
  • the above-mentioned embodiment forms the case 50 in the lithium-ion secondary battery 1 by folding a single composite package film 53 and sealing the fringes 51 B and 52 B together, the case 50 can also be formed by arranging two composite package films such that they oppose each other and sealing their fringes to each other.
  • lithium-ion secondary batteries of Examples 1 to 18 and Comparative Examples 1 to 13 each configured similar to the lithium-ion secondary battery 1 shown in FIG. 1 were made.
  • an anode was made. Initially, for making the anode, artificial graphite (90 parts by mass) as an anode active material, carbon black (2 parts by mass) as a conductive auxiliary agent, and polyvinylidene (PVDF) (8 parts by mass) as a binder were mixed and dispersed into N-methyl-pyrrolidone (NMP), so as to yield a slurry. Thus obtained slurry was applied by doctor blading to an electrodeposited copper foil acting as a collector, and was dried at 110° C. After being dried, the slurry was extended, so as to yield the anode.
  • NMP N-methyl-pyrrolidone
  • carbon black (6 parts by mass) as a conductive auxiliary agent, and PVDF (4 parts by mass) as a binder were mixed and dispersed into NMP, so as to yield a slurry.
  • slurry was applied to an aluminum foil acting as a collector, dried, and extended, so as to yield the cathode.
  • a nonaqueous electrolytic solution was prepared.
  • a mixture of propylene carbonate (PC), ethylene carbonate (EC), and diethyl carbonate (DEC) at a volume ratio of 2:1:7 as a solvent
  • LiPF 6 was added as a solute to the solvent.
  • LiPF 6 was added such that its concentration became 1.5 mol/dm ⁇ 3 .
  • 1,3-propane sultone was added so as to become 5 mass % with respect to the total mass of the finally obtained solution
  • vinylene carbonate (VC) was added so as to become 0.5 mass % with respect to the total mass of the finally obtained solution, whereby the nonaqueous electrolytic solution was obtained.
  • anode and cathode were laminated with a separator made of polyethylene interposed therebetween, so as to yield a laminate (matrix).
  • a laminate matrix
  • laminate was put into an aluminum laminate pack having an opening.
  • the fringes forming the opening were sealed together under vacuum, so as to make a lithium-ion secondary battery (having a length of 115 mm, a width of 87 mm, and a thickness of 3 mm).
  • a composite package film made of a laminate in which an innermost layer made of a synthetic resin (layer made of denatured polypropylene) in contact with the nonaqueous electrolytic solution, a metal layer made of an aluminum foil, and a layer made of polyamide were successively laminated in this order was used.
  • Two such composite package films were overlaid on each other, and their fringes were heat-sealed, so as to make the aluminum laminate pack.
  • Lithium-ion secondary batteries of Examples 2 to 17 and Comparative Examples 1 to 13 were made as in Example 1 except that the volume ratio of PC, EC, and DEC used in the solvent of the nonaqueous electrolytic solution and the amounts of addition of PS and VC were changed as shown in Tables 1 and 2.
  • the lithium-ion secondary battery of Example 18 was made as in Example 1 except that the volume ratio of PC, EC, DEC, and EMC used in the solvent of the nonaqueous electrolytic solution and the amounts of addition of PS and VC were set as shown in Table 1.
  • each lithium-ion secondary battery was initially charged at 25° C., and was discharged immediately thereafter.
  • the initial charging/discharging characteristic was evaluated according to the ratio between the charging capacity and discharging capacity at that time.
  • For charging constant-current constant-voltage charging was performed at 0.2 C (500 mA) up to 4.2 V.
  • For discharging constant-current discharging was carried out at 0.2 C until the voltage became 2.5 V.
  • Tables 3.1, 3.2, and 4 show thus obtained results. In Tables 3.1, 3.2, and 4, batteries exhibiting a value of 80% or higher in the results of initial charging/discharging characteristic were evaluated as those having a practically sufficient initial charging/discharging characteristic.
  • the high-rate discharging characteristic was evaluated according to the ratio between the discharging capacity (A 2C ) at the time of constant-current discharging at 2 C (5000 mA) and the discharging capacity (A 0.5C ) at the time of constant-current discharging at 0.5 C (1250 mA) at 25° C.
  • Tables 3.1, 3.2, and 4 show thus obtained results.
  • batteries exhibiting a value of 50% or higher in the results of high-rate discharging characteristic were evaluated as those having a practically sufficient high-rate discharging characteristic.
  • each lithium-ion secondary battery was subjected to 300 cycles of charging and discharging at 25° C., and then its discharging capacity A2 was measured.
  • the charging/discharging cycle characteristic was evaluated according to the ratio [100 ⁇ (A2/A1)][%] between the discharging capacity A1 after the initial charging and discharging and A2.
  • For charging constant-current constant-voltage charging was performed at 1 C (2500 mA) up to 4.2 V.
  • For discharging, constant-current discharging was carried out at 1 C until the voltage became 2.5 V.
  • Tables 3.1, 3.2, and 4 show thus obtained results. In Tables 3.1, 3.2, and 4 batteries exhibiting a value of 80% or higher in the results of charging/discharging cycle characteristic were evaluated as those having a practically sufficient charging/discharging cycle characteristic.
  • the present invention can provide a nonaqueous electrolytic solution which can easily and reliably construct a lithium-ion secondary battery capable of attaining excellent initial power generation efficiency, high-rate discharging characteristic, and charging/discharging cycle characteristic, while being able to achieve an excellent reliability even when stored or caused to generate power within the range of 40 to 100° C.
  • the present invention can provide a high-performance lithium-ion secondary battery capable of attaining excellent initial power generation efficiency, high-rate discharging characteristic, and charging/discharging cycle characteristic, while being able to achieve an excellent reliability even when stored or caused to generate power within the range of 40 to 100° C.

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CN110010850A (zh) * 2005-10-20 2019-07-12 三菱化学株式会社 锂二次电池以及其中使用的非水电解液
KR100812056B1 (ko) * 2005-10-24 2008-03-07 주식회사 엘지화학 레독스 셔틀제의 수명 감소 억제제, 이를 포함하는 비수전해액 및 이차전지
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KR100810601B1 (ko) * 2006-12-29 2008-03-06 새한에너테크 주식회사 대면적 2차전지용 크루드 셀 및 그 제조방법
US9196922B2 (en) * 2007-02-08 2015-11-24 Lg Chem, Ltd. Lithium secondary battery of improved high-temperature cycle life characteristics
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US20110039163A1 (en) * 2009-03-31 2011-02-17 Masaki Deguchi Non-aqueous electrolyte and non-aqueous electrolyte secondary battery using the same
JP2010277827A (ja) * 2009-05-28 2010-12-09 Sony Corp 非水電解液、正極およびそれらを用いた非水電解質二次電池
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KR20120036882A (ko) 2010-03-29 2012-04-18 파나소닉 주식회사 비수 전해질 및 그것을 사용한 비수 전해질 이차전지
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CN103066331B (zh) * 2012-11-29 2018-06-15 湖北龙能新能源科技股份有限公司 一种超低温高倍率型锂离子电池的制备方法
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US20170309963A1 (en) * 2014-11-11 2017-10-26 Dow Global Technologies Llc High volumetric energy density lithium battery with long cycle life
WO2020184692A1 (ja) * 2019-03-12 2020-09-17 大日本印刷株式会社 全固体電池用外装材、全固体電池及びその製造方法

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